Patent GB-1002454-A (GB)
Title: New nitrogen-containing hardeners for epoxy resins
Inventor: STARK BERNARD PETER
IPC: C08G59/54
Filed: 1963-02-28
Abstract: As hardening agents for epoxy resins, use is made of reaction products of polyamines of the formula H2N(CHR-CH2-NH)mH, in which R is hydrogen or an alkyl group of up to six carbonatoms and m is 1-6, with compounds of the formula <FORM:1002454/C3/1> in which X represents an oxygen atom or a group -NH-, Y represents a substituted or unsubstituted divalent aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue, n is 0 or 1, Z represents, when n is 1, an alkoxy, aryloxy, cycloalkoxy or aralkoxy group and, when n is O, an alkoxy, aryloxy, cycloalkyloxy or aralkoxy group or a group having a carbon-carbon double bond conjugated with the carbonyl group in the formula, preferably a group of the formula -C(R5) : CHR6, in which R5 and R6 may be hydrogen atoms or substituted or unsubstituted alkyl, aryl, cycloalkyl or aralkyl hydrocarbon residues, and R1, R2, R3 and R4\t are hydrogen or halogen atoms or substituted or unsubstituted aliphatic or aromatic hydrocarbon groups, or one of R2 and R3 may represent an alkoxy, aryloxy, acyloxy, amino, acylamino, carboxyl, alkoxycarbonyl, alkylcarbonyl or formyl group, the other representing a hydrogen atom or a similar group, or R2 and R3 together may represent a substituted or unsubstituted hydrocarbon chain, particularly -CH2CH : CH-(see Division C2).  Examples are given of the manufacture of products from (1) ethyl a -(dihydrodicyclopentadienyloxy) propionate and triethylenetetramine, diethylenetriamine and tetraethylene - pentamine; (2) ethyl dihydrodicyclopentadienyl - oxyacetate and triethylenetetramine, (3) methyl p - (dihydrodicyclopentadienyloxy) benzoate and triethylenetetramine; (4) dihydrodicyclopentadienyl methacrylate and triethylenetetramine, (5) N-exo-(dihydrodicyclopentadienyl) acrylamide and triethylenetetramine, (6) ethyl a  - (bicyclo-[2,2,1] - hept - 2 - yloxy) - propionate and triethylenetetramine; (7) triethylenetetramine and a reaction product of ethyl lactate and methyl bicyclo - (2,2,1) - hept - 5 - en - 2 - carboxylate; (8) triethylenetetramine and a reaction product of ethyl lactate and phenyl bicyclo - (2,2,1) - hept - 5 - en - 2 - yl methyl ether; (9) N - exo - (dihydrodicyclopentadienyl)-methacrylamide and triethylenetetramine; (10) triethylenetetramine and a reaction product of ethyl lactate and bicyclo - (2,2,1) - hept - 5 - en-2-yl acetate; (11) triethylenetetramine and a reaction product of acrylonitrile and bicyclo-(2,2,1)-hept-2-ene, and (12) triethylenetetramine and a reaction product of methyl methacrylate and bicyclo-(2,2,1)-hepten-2-ol.  The epoxy resins may be polyglycidyl esters or ethers, a number of both of which are specified, and the resulting compositions may contain fillers, plasticizers or colouring agents, a number of which are also specified.  Comparative examples of the use of some of the products are given.ALSO:The invention relates to reaction products of polyamines of the formula H2N(CHR-CH2-NH)mH in which R is hydrogen or an alkyl group of up to six carbon atoms and m is 1-6, with compounds of the formula <FORM:1002454/C2/1> in which X represents an oxygen atom or a group -NH-, Y represents a substituted or unsubstituted divalent aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue, n is 0 or 1, Z represents, when n is 1, an alkoxy, aryloxy, cycloalkoxy or aralkoxy group and, when n is O, an alkoxy, aryloxy, cycloalkyloxy or aralkoxy group or a group having a carboncarbon double bond conjugated with the carbonyl group in the formula, preferably a group of the formula -C(R5) : CHR6, in which R5 and R6 may be hydrogen atoms or substituted or unsubstituted alkyl, aryl, cycloalkyl or aralkyl hydrocarbon residue, and R1, R2, R3 and R4 are hydrogen or halogen atoms or substituted or unsubstituted aliphatic or aromatic hydrocarbon groups, or one of R2 and R3 may represent an alkoxy, aryloxy, acyloxy, amino, acylamino, carboxyl, alkoxycarbonyl, alkylcarbonyl or formyl group, the other representing a hydrogen atom or a similar group, or R2 and R3 together may represent a substituted or unsubstituted hydrocarbon chain, particularly -CH2CH: CH-. The reaction may be performed by mixing the reagents, suitably in an inert atmosphere, and unreacted polyamine may be removed by distillation after the reaction. Products in which n is 1, X represents oxygen and Z represents a lower alkoxy group may also be prepared by reacting an ester of a hydroxycarboxylic acid, a number of which are specified, with a compound of the formula <FORM:1002454/C2/2> preferably in the presence of an acid catalyst. The preferred compound of Formula II is dicyclopentadiene, but other compounds may be prepared by addition of cyclopentadiene to an olefine of the formula R1(R2)C = C(R3)R4, in which R1, R2, R3 and R4 are as above. Examples are given of the manufacture of products from (1) ethyl a -(dihydrodicyclopentadienyloxy) propionate and triethylenetetramine, diethylenetriamine and tetraethylenepentamine; (2) ethyl dihydrodicyclopentadienyloxyacetate and triethylenetetramine; (3) methyl p - (dihydrodicyclopentadienyloxy) benzoate and triethylenetetramine; (4) dihydrodicyclopentadienyl methacrylate and triethylenetetramine; (5) N-exo-(dihydrodicyclopentadienyl)-acrylamide and triethylenetetramine, (6) ethyl a  - (bicyclo - [2,2,1]hept - 2 - yloxy) propionate (from ethyl lactate and norbornylene) and triethylene tetramine; (7) triethylene tetramine and a reaction product of ethyl lactate and methyl bicyclo (2,2,1)-hept-5-en-2-carboxylate, (8) triethylenetetramine and a reaction product of ethyl lactate and phenyl bicyclo-(2,2,1)-hept-5-en-2-yl methyl ether, (9) N-exo-(dihydrodicyclopentadienyl)-methacrylamid and triethylenetetramine, (10) triethylenetetramine and a reaction product of ethyl lactate and bicylo-(2,2,1)-hept-5-en-2-yl acetate, (11) triethylenetetramine and a reaction product of acrylonitrile and bicyclo-(2,2,1)-hept-2-ene, and (12) triethylenetetramine and a reaction product of methyl methacrylate and bicyclo-(2,2,1)-hepten-2-ol. The products are useful as hardening agents for epoxy resins (see Division C3).